CN102643441A - Method for preparing polyaspartic acid type hydrogel - Google Patents
Method for preparing polyaspartic acid type hydrogel Download PDFInfo
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- CN102643441A CN102643441A CN2012101353764A CN201210135376A CN102643441A CN 102643441 A CN102643441 A CN 102643441A CN 2012101353764 A CN2012101353764 A CN 2012101353764A CN 201210135376 A CN201210135376 A CN 201210135376A CN 102643441 A CN102643441 A CN 102643441A
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Abstract
The invention relates to a method for preparing polyaspartic acid type hydrogel, which includes: utilizing water as reaction medium, mixing organic base and polysuccinimide to react and obtaining polyaspartic acid type hydrogel. The method for preparing polyaspartic acid type hydrogel is few in operation steps and chemical reagent, simple and flexible in process, low in cost and high in reaction speed and has no pollution to the environment.
Description
Technical field
The invention belongs to the macromolecule hydrogel preparing technical field, relate to a kind of method for preparing polyaspartic acid hydrogels, specifically, relating to a kind of is the method for feedstock production polyaspartic acid hydrogels with the polysuccinimide.
Background technology
Super-strong moisture absorbing property hydrogel is that a kind of can absorb water tens times even several thousand times are to the polymkeric substance of own wt.The SAP 73 hydrogel is to be skeleton with the SAP 73, and through being cross-linked to form the polymkeric substance of network-like structure, it has higher water absorbing properties, good biodegradability and biocompatibility.It is widely used in the key areas such as sustained release of health care product, agriculture water-holding agent, wastewater treatment, chemical at present.
It is feedstock production SAP 73 hydrogel method that Chinese patent CN1814650A, CN1198444A and CN1422886A disclose with the polysuccinimide.These methods all are that polysuccinimide is dissolved in N, and in dinethylformamide (DMF) or DMSO 99.8MIN. (DMSO) equal solvent, after crosslinked and separation and purification, the SAP 73 hydrogel is processed in hydrolysis in alkaline solution.These preparing method's processes are complicated, and the consumption of organic solvent that is adopted is big, and harmful to the person, contaminate environment; Reclaim the complex procedures of organic solvent, cost is high, also produces secondary pollution simultaneously.
Chinese patent CN 1631517A abandons DMF with an organic solvent, adopts the water medium legal system to be equipped with the SAP 73 hydrogel.This method is raw material with the polysuccinimide, is linking agent with a kind of in the polyamines organic basess such as diamines or triamine, tetramine or two kinds and two or more mixtures, preparation cross-linked poly-aspartic acid hydrogel in alkaline aqueous solution.Use a large amount of alkali in its process, when having improved cost, also can cause certain pollution environment.
Therefore, it is more cheap to research and develop out a kind of cost at present, and the SAP 73 hydrogel production technique that can not pollute environment.
Summary of the invention
Technical problem to be solved by this invention is the deficiency to above-mentioned prior art, and a kind of method for preparing polyaspartic acid hydrogels is provided.As reaction medium, operation steps is few with water for this method, and the chemical reagent of use is few, the technology simple and flexible, and with low cost, speed of response is very fast, and can not pollute environment.
To achieve these goals; The invention provides a kind of method for preparing polyaspartic acid hydrogels; Said method is that organic bases and polysuccinimide raw material are carried out hybrid reaction; Make polyaspartic acid hydrogels, wherein, the mol ratio of organic bases and polysuccinimide raw material is 10:1 ~ 1:10.
In a preferred embodiment of the invention, the mol ratio of said organic bases and polysuccinimide raw material is 2:1 ~ 1:2.
According to the inventive method, said organic bases is solid organic alkali or liquid organic bases or organic bases solution.Said organic bases solution be by solid organic alkali or liquid organic bases with process after water solvent mixes, wherein, the weight ratio of solid organic alkali or liquid organic bases and water solvent is 1:10 ~ 1:200.
In one embodiment of the invention, said organic bases is diamines and/or polyamines class material, and it is selected from Hydrazine Hydrate 80, quadrol, tn, tetramethylenediamine, hexanediamine, Methionin and the lysine salt one or more.Said water solvent is a deionized water or by deionized water and the formulated neutral brine solution of salt, the concentration of said neutral brine solution is 0.1 ~ 1mol/L, and said salt is selected from urea, NaCl, KCl, KNO
3, NaNO
3, K
2SO
4, Na
2SO
4, in the phosphoric acid salt one or more.
According to the inventive method; Said polysuccinimide raw material is polysuccinimide particulate or polysuccinimide suspension slurry; Wherein, The polysuccinimide suspension slurry be by the polysuccinimide particulate with process after water solvent mixes, the weight ratio of polysuccinimide particulate and water solvent is 1:5 ~ 1:500.
In one embodiment of the invention, the weight ratio of said polysuccinimide particulate and water solvent is 1:50 ~ 1:100.The particle diameter of said polysuccinimide particulate is 100 ~ 400 orders, and its weight-average molecular weight is 50, more than the 000Da (dalton).Said water solvent is a deionized water or by deionized water and the formulated neutral brine solution of salt, the concentration of said neutral brine solution is 0.1 ~ 1mol/L, and said salt is selected from urea, NaCl, KCl, KNO
3, NaNO
3, K
2SO
4, Na
2SO
4, in the phosphoric acid salt one or more.
According to the inventive method; It is said that organic bases and polysuccinimide raw material are carried out hybrid reaction is that reactant A once or is several times joined in the reactant B; Wherein, reactant A is organic bases or polysuccinimide raw material, and reactant B is polysuccinimide raw material or organic bases.
When joining reactant A in the reactant B several times, the add-on of each reactant A is equivalent or inequality, equates or does not wait pitch time.
In one embodiment of the invention, said hybrid reaction mode comprises that liquid phase mixes reaction or wet grinding hybrid reaction, and wherein, stirring comprises mechanical stirring or magnetic agitation.
According to the inventive method, mix when reaction carrying out liquid phase, temperature of reaction is 0 ~ 90 ℃, the reaction times is 1min ~ 1h.When carrying out the wet grinding hybrid reaction, the stirring revolution of shredder is 25000r/min.Reaction times is 10min ~ 10h.
In a preferred embodiment of the invention, mix when reaction carrying out liquid phase, temperature of reaction is 50 ~ 60 ℃, and the reaction times is 10 ~ 30min.When carrying out the wet grinding hybrid reaction, the reaction times is 2 ~ 6h.
According to the inventive method; Said polyaspartic acids hydrogel makes solid polyaspartic acids hydrogel after drying; Said drying is dry again after separating out with polyaspartic acids hydrogel convection drying or with ethanol; Said drying means comprises forced air drying, lyophilize, seasoning or spraying drying.The temperature of said forced air drying is 30 ~ 90 ℃.
In a specific embodiment of the present invention; With the organic bases that contains two amino at least (for example, organic bases can be selected from Hydrazine Hydrate 80, quadrol, tn, tetramethylenediamine, hexanediamine, Methionin and lysine salt) with process organic bases solution after deionized water or neutral brine solution mix according to the weight ratio of 1:1 ~ 1:100; Is 50 with this solution according to organic bases and weight-average molecular weight; The above polysuccinimide particulate of 000Da is the mixed of 1:2 ~ 2:1 according to mol ratio, under 50 ~ 60 ℃ of temperature, carries out liquid phase and mixes reaction, in the reaction process; Can improve temperature of reaction through the mode of common heating or microwave heating; Adopt magnetic agitation or churned mechanically mode to carry out hybrid reaction, behind reaction times 1 ~ 60min, make polyaspartic acid hydrogels; With the polyaspartic acid hydrogels that is obtained forced air drying 8 ~ 24h under 40 ~ 60 ℃ of temperature, or forced air drying 2 ~ 10h again after separating out with ethanol.
In another specific embodiment of the present invention, under agitation condition, polysuccinimide is added in the entry, behind the thorough mixing, make the polysuccinimide suspension slurry; Then, with the organic bases that contains two amino at least (for example, organic bases can be selected from Hydrazine Hydrate 80, quadrol, tn, tetramethylenediamine, hexanediamine, Methionin and lysine salt) or its aqueous solution several times; Or dropwise be added in the polysuccinimide suspension slurry; Organic bases and weight-average molecular weight are 50, and the mol ratio of the polysuccinimide that 000Da is above is 1:10 ~ 10:1, under 50 ~ 60 ℃ of temperature; Reaction 1 ~ 60min makes polyaspartic acid hydrogels; With the polyaspartic acid hydrogels that is obtained forced air drying 8 ~ 24h under 40 ~ 60 ℃ of temperature, or forced air drying 2 ~ 10h again after separating out with ethanol.
In another specific embodiment of the present invention; With the organic bases that contains two amino at least (for example; Organic bases can be selected from Hydrazine Hydrate 80, quadrol, tn, tetramethylenediamine, hexanediamine, Methionin and lysine salt) or its aqueous solution is several times, or dropwise be added in polysuccinimide particulate or the suspension slurry, organic bases and weight-average molecular weight are 50; The mol ratio of the polysuccinimide that 000Da is above is 1:10 ~ 10:1; In shredder, carry out wet grinding 2 ~ 6h, then, prepared polyaspartic acid hydrogels is placed forced air drying 8 ~ 24h under 40 ~ 60 ℃ of temperature.
The water-intake rate (swelling ratio) that the present invention measures the SAP 73 hydrogel adopts the tea bag method.Operation steps is following:
Under the condition of 23 ℃ of temperature, humidity 50%,, immerse in the deionized water the polyaspartic acid hydrogels sample that the prepares tea bag (diameter is the circle closing in tea bag of 400ram) of packing into; In the certain hour interval, take out tea bag, draining 15min in air, weighing is designated as Wt; Blank tea bag with corresponding repeats above-mentioned steps; Weighing is designated as Wo, and example weight is designated as Ws, and sample water-intake rate R is by computes:
R=(Wt-Wo-Ws)/Ws (the dried glue of unit: g/g)
Technical scheme of the present invention is to be 50 with weight-average molecular weight; Above polysuccinimide and the organic bases of 000Da reacts in water medium; Organic bases can be opened the five-ring of polysuccinimide fast, makes the water-soluble continuous increase of water-fast polysuccinimide particulate originally, when the molecule of PSI constantly stretches winding mutually; Organic bases can play crosslinked action with being connected between same PSI molecule different loci or the different PSI molecules.In fact, the speed of response of this process is exceedingly fast, and crosslinked hydrolytic process is almost carried out simultaneously.
Simultaneously, the present invention only makes water or neutral brine solution as solvent, does not use other any organic solvents.Avoid the use of a large amount of poisonous organic solvents, also avoided Recovery of Organic Solvent.Having avoided with an organic solvent simultaneously, also avoided the use mineral alkali, do not use other materials, simplified technology greatly, improved production efficiency, saved raw material, and the production of the few waste water of alkali greatly.
Embodiment
To combine embodiment to specify the present invention below, these embodiment only play the illustrative effect, do not limit to range of application of the present invention.
Embodiment
Embodiment 1:
With weight-average molecular weight is 500; After the polysuccinimide of 000Da (PSI) raw material pulverizing, taking by weighing particle diameter is 100 ~ 400 purpose PSI particulate 2g, adds deionized water as water solvent according to the amount of PSI: water solvent=1:100 (weight ratio); Uniform mixing is mixed with the PSI suspension slurry; The Hydrazine Hydrate 80 that takes by weighing 80wt% according to the amount of organic bases: PSI=1:1 (mol ratio) is put into the beaker of 250ml as organic bases, and adds water solvent according to the amount of organic bases: water solvent=1:200 (weight ratio), and uniform mixing is mixed with organic bases solution; Under 50 ℃ of conditions, while stirring the PSI suspension slurry is joined in the organic bases solution, stirring reaction 10min puts into baking oven with the product that is obtained, and forced air drying 8h under 40 ℃ of conditions makes exsiccant white polyaspartic acid hydrogels.Under the condition of 23 ℃ of temperature, humidity 50%, adopt the tea bag method to measure the water-intake rate of polyaspartic acid hydrogels in the NaCl of deionized water and the 0.9wt% aqueous solution, the result sees table 1.
Embodiment 2:
What embodiment 2 and embodiment 1 were different is that the molecular weight of PSI raw material is 100,000Da, PSI: water solvent=1:50 (weight ratio); Organic bases: PSI=10:1 (mol ratio), organic bases: water solvent=1:100 (weight ratio); Temperature of reaction is 90 ℃, and the stirring reaction time is 1h; All the other conditions are identical with embodiment 1, and measure the water-intake rate of polyaspartic acid hydrogels according to the method identical with embodiment 1, and the result sees table 1.
Embodiment 3:
What embodiment 3 and embodiment 1 were different is PSI: water solvent=1:100 (weight ratio); Organic bases adopts quadrol, organic bases: water solvent=1:50 (weight ratio), and organic bases total amount: PSI=1:2 (mol ratio), temperature of reaction is 20 ℃, while stirring organic bases solution is joined in the PSI suspension slurry, the stirring reaction time is 2h; All the other conditions are identical with embodiment 1, and measure the water-intake rate of polyaspartic acid hydrogels according to the method identical with embodiment 1, and the result sees table 1.
Embodiment 4:
What embodiment 4 and embodiment 1 were different is, the molecular weight of PSI raw material is 50,000Da, and PSI participates in reaction with particulate; Organic bases adopts tetramethylenediamine, and water solvent adopts the urea soln of 0.1mol/L, PSI: water solvent=1:5 (weight ratio), organic bases: PSI=1:10 (mol ratio), organic bases: water solvent=1:10 (weight ratio); Under the room temperature condition, in the shredder that the PSI particulate is added, with the rotating speed of 25000r/min while grinding dropwise with in the organic bases solution adding PSI particulate, griding reaction 1h; All the other conditions are identical with embodiment 1, and measure the water-intake rate of polyaspartic acid hydrogels according to the method identical with embodiment 1, and the result sees table 1.
Embodiment 5:
What embodiment 5 and embodiment 6 were different is, the molecular weight of PSI raw material is 100, and the 000Da water solvent adopts the NaCl solution of 1mol/L, PSI: water solvent=1:500 (weight ratio); Organic bases adopts hexanediamine, organic bases: PSI=5:1 (mol ratio); Temperature of reaction is 0 ℃, and organic bases solution PSI suspension slurry divides by constant duration not and progressively joins PSI for 3 ~ 5 times and suspend in the night organic bases solution, and the stirring reaction time is 5h; All the other conditions are identical with embodiment 1, and measure the water-intake rate of polyaspartic acid hydrogels according to the method identical with embodiment 1, and the result sees table 1.
Embodiment 6:
What embodiment 6 and embodiment 1 were different is that the molecular weight of PSI raw material is 50,000Da, PSI: water solvent=1:100 (weight ratio); Organic bases adopts Methionin, organic bases: PSI=1:5 (mol ratio); Under 90 ℃ of conditions, while stirring organic bases solution is progressively joined for 3 ~ 5 times in the PSI suspension slurry by dividing at interval equal time, the stirring reaction time is 10h; All the other conditions are identical with embodiment 1, and measure the water-intake rate of polyaspartic acid hydrogels according to the method identical with embodiment 1, and the result sees table 1.
Embodiment 7:
What embodiment 7 and embodiment 1 were different is that the molecular weight of PSI raw material is 100,000Da, PSI: water solvent=1:5 (weight ratio); Organic bases adopts quadrol and Hydrazine Hydrate 80 mixture, and the mol ratio of quadrol and Hydrazine Hydrate 80 is 1:4, organic bases: water solvent=1:10 (weight ratio) organic bases total amount: PSI=2:1 (mol ratio); Under the room temperature condition, in the shredder that the PSI particulate is added, with the rotating speed of 25000r/min while grinding dropwise with in the organic bases solution adding PSI particulate, griding reaction 5h; All the other conditions are identical with embodiment 1, and measure the water-intake rate of polyaspartic acid hydrogels according to the method identical with embodiment 1, and the result sees table 1.
Embodiment 8:
What embodiment 8 and embodiment 1 were different is PSI: water solvent=1:50 (weight ratio); Organic bases adopts hexanediamine and Hydrazine Hydrate 80 mixture, and the mol ratio of hexanediamine and Hydrazine Hydrate 80 is 1:4, organic bases: water solvent=1:100 (weight ratio); Organic bases total amount: PSI=2:1 (mol ratio); Under 60 ℃ of conditions, while stirring organic bases solution is joined in the PSI suspension slurry, the stirring reaction time is 30min; All the other conditions are identical with embodiment 1, and measure the water-intake rate of polyaspartic acid hydrogels according to the method identical with embodiment 1, and the result sees table 1.
Table 1
Claims (10)
1. method for preparing polyaspartic acid hydrogels; Said method is that organic bases and polysuccinimide raw material are carried out hybrid reaction; Make polyaspartic acid hydrogels, wherein, the mol ratio of organic bases and polysuccinimide raw material is 10: 1～1: 10.
2. method according to claim 1 is characterized in that: the mol ratio of said organic bases and polysuccinimide raw material is 2: 1～1: 2.
3. method according to claim 1 and 2 is characterized in that:
Said organic bases is solid organic alkali or liquid organic bases or organic bases solution;
Said organic bases solution be by solid organic alkali or liquid organic bases with process after water solvent mixes, wherein, the weight ratio of solid organic alkali or liquid organic bases and water solvent is 1: 10～1: 200.
4. method according to claim 3 is characterized in that:
Said organic bases is diamines and/or polyamines class material, and it is selected from Hydrazine Hydrate 80, quadrol, tn, tetramethylenediamine, hexanediamine, Methionin and the lysine salt one or more;
Said water solvent is a deionized water or by deionized water and the formulated neutral brine solution of salt, the concentration of said neutral brine solution is 0.1～1mol/L, and said salt is selected from urea, NaCl, KCl, KNO
3, NaNO
3, K
2SO
4, Na
2SO
4, in the phosphoric acid salt one or more.
5. method according to claim 1 and 2 is characterized in that:
Said polysuccinimide raw material is polysuccinimide particulate or polysuccinimide suspension slurry; Wherein, The polysuccinimide suspension slurry be by the polysuccinimide particulate with process after water solvent mixes, the weight ratio of polysuccinimide particulate and water solvent is 1: 5～1: 500.
6. method according to claim 5 is characterized in that:
The weight ratio of said polysuccinimide particulate and water solvent is 1: 50～1: 100;
The particle diameter of said polysuccinimide particulate is 100～400 orders, and its weight-average molecular weight is 50, more than the 000Da;
Said water solvent is a deionized water or by deionized water and the formulated neutral brine solution of salt, the concentration of said neutral brine solution is 0.1～1mol/L, and said salt is selected from urea, NaCl, KCl, KNO
3, NaNO
3, K
2SO
4, Na
2SO
4, in the phosphoric acid salt one or more.
7. method according to claim 1 and 2 is characterized in that:
Said organic bases and polysuccinimide raw material are carried out hybrid reaction is that reactant A once or is several times joined in the reactant B, and wherein, reactant A is organic bases or polysuccinimide raw material, and reactant B is polysuccinimide raw material or organic bases;
When joining reactant A in the reactant B several times, the add-on of each reactant A is equivalent or inequality, equates or does not wait pitch time.
8. method according to claim 7 is characterized in that: said hybrid reaction mode comprises that liquid phase mixes reaction or wet grinding hybrid reaction, and wherein, stirring comprises mechanical stirring or magnetic agitation.
9. method according to claim 8 is characterized in that:
Mix when reaction carrying out liquid phase, temperature of reaction is 0～90 ℃, and the reaction times is 1min～1h;
When carrying out the wet grinding hybrid reaction, the stirring revolution of shredder is 25000r/min, and the reaction times is 10min～10h.
10. method according to claim 9 is characterized in that:
Mix when reaction carrying out liquid phase, temperature of reaction is 50～60 ℃, and the reaction times is 10～30min;
When carrying out the wet grinding hybrid reaction, the reaction times is 2～6h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968389A (en) * | 2016-06-20 | 2016-09-28 | 北京化工大学 | Polyaspartic acid/polyacrylic acid interpenetrating network hydrogel and preparation method thereof |
| CN108641724A (en) * | 2018-05-25 | 2018-10-12 | 钱兴 | A kind of preparation method of water-loss reducer of soil |
| CN111333871A (en) * | 2020-04-06 | 2020-06-26 | 刘云晖 | Intrinsic self-repairing zwitterionic hydrogel and preparation method thereof |
| CN112408844A (en) * | 2020-12-04 | 2021-02-26 | 河北协同环保科技股份有限公司 | Gypsum retarder and preparation method and application thereof |
| CN114058022A (en) * | 2021-12-21 | 2022-02-18 | 郑州沃尔德农业科技有限公司 | Amino acid slow-release fertilizer water-retaining agent, preparation method and application method |
| CN115785922A (en) * | 2022-09-13 | 2023-03-14 | 长江大学 | High-temperature water-based drilling fluid for ultra-large displacement well |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105968389A (en) * | 2016-06-20 | 2016-09-28 | 北京化工大学 | Polyaspartic acid/polyacrylic acid interpenetrating network hydrogel and preparation method thereof |
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| CN108641724A (en) * | 2018-05-25 | 2018-10-12 | 钱兴 | A kind of preparation method of water-loss reducer of soil |
| CN111333871A (en) * | 2020-04-06 | 2020-06-26 | 刘云晖 | Intrinsic self-repairing zwitterionic hydrogel and preparation method thereof |
| CN112408844A (en) * | 2020-12-04 | 2021-02-26 | 河北协同环保科技股份有限公司 | Gypsum retarder and preparation method and application thereof |
| CN114058022A (en) * | 2021-12-21 | 2022-02-18 | 郑州沃尔德农业科技有限公司 | Amino acid slow-release fertilizer water-retaining agent, preparation method and application method |
| CN115785922A (en) * | 2022-09-13 | 2023-03-14 | 长江大学 | High-temperature water-based drilling fluid for ultra-large displacement well |
| CN115785922B (en) * | 2022-09-13 | 2023-08-22 | 长江大学 | Super-large displacement well high-temperature water-based drilling fluid |
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